Printing paste and process of decorating textile therewith



PRINTING PASTE AND PROCESS OF DECORAT- ING TEXTILE THEREWITH WilhelmGraulich, Leverkusen-Bayerwerk, Wilhelm Becker, Leverkusen, and OttoBayer, Leverkusen- Bayerwerk, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany 'NoDrawing. Application December 27, 1956 Serial No. 630,751

Claims priority, application Germany August 22, 1951 12 Claims. (Cl.260--29.6)

The present invention relates to the printing and decorating of fibroussheet material, more particularly to a new and improved printing processand printing paste. This applicationis a continuation-in-part of SerialNo. 304,846, filed August 2, 1952.

It is known in the printing of fibrous sheet material according to thepigment printing process to employ poly mer latices, which contain asbinders vinylidene compounds, such aspolyvinyl acetate, methyl or ethylmethacrylate and butadiene, and their copolymers with each other,furthermore combinations of polyvinyl compounds with thermosettingresins.

Especially suitable for these purposes are the copolymer emulsions inwhich the copolymers contain monomers on the one hand, which whenpolymerized per se represent typical film formers, and monomers on theother hand, which are cross-linking agents for the film formers. Theprints obtained with these latices ordinarily satisfy most requirements,the fastness to rubbing and washing of prints obtained with theselatices according to the latter process being of special importance.

It is an object of the invention to provide a novel printingpaste and aprocess for its application, with which the printing or decorating offibrous sheet material and paper may be carried out with excellentresults.

Further objects will become apparent as the following descriptionproceeds.

We have found that excellent results are obtained in the printing offibrous sheet material according to the pigment printing process bymeans of polymer emulsions when using emulsions of copolymers which areobtained from polymerisable viny'lidene compounds containing reactivegroups on the one hand, and polymerizable vinyl or divinyl compoundsimparting to the final product elastic properties on the other hand, andreacting said vinyl or divinyl compounds on fixing the printing designswith polyfunctional compounds which are capable of reacting with thereactive groups of the copolymers.

The term polymerizable vinylidene compounds containing reactive groupsis intended to comprise acrylic acid and methacrylic acid, acrylic amideand methacrylic amide which may be substituted by alkyl groups such asmethyl, butyl, hexyl, dodecyl, unsaturated kctones such as vinyl methylketone, u-substituted acroleins, such as a-ethyl acrolein and a-chloroacrylates, such as methyl, butyl, hexyl, a-chloro acrylate and vinylcompounds containing amino groups, for instance, the addition compoundof 1 mol of a primary amine to 1 mol ofhexa-hydro-l,3,5-triacrylyl-s-triazine.

The above said polymerizable vinylidene compounds containing reactivegroups are copolymerized according to the invention with vinyl compoundsimparting to the polymers elastic properties, particularly acrylates andmethacrylates of alcohols having at least 4 carbon atoms such as thebutyl, hexyl, dodecyl esters and furthermore by weight.

2,908,658 Patented Oct. 13, 1959 7 2 butadienes and chloro butadieneswhich also impart elastic properties to the final products.

' Furthermore the copolymers may contain still other components such asstyrene, acrylonitrile, 1.1-dichloroethene. The copolymers may furthercontain other polymerizable .vinyl components which may simultaneouslyact as cross-linking agents, for instance the diacrylates of ethyleneglycol.

As polyfunctional, cross-linking compounds which are capable of reactingwith the reactive groups of the copolymers may be named the so-calledpolyisocyanate-formers, i.e. compounds reacting like polyfunctionalisocyanates at elevated temperature (of. French Patent No. I

876,285).- As examples may be mentioned the addition products of 1 molof a diisocyanate and 2 mols of a 1.3-diketone or 1.3-ketone ester likeacetic esters and malonic acid esters. Especially well suited are theaddition products of bisulfites and polyfunctional isocyanates whichpossess the advantage of being water-soluble. Furthermore, formaldehyde,its various polymeric modifications and substances yielding formaldehydesuch as sodium formaldehyde sulfoxylate may be utilized in practicingthe invention. Another example of cross-linking agents which may beemployed in the herein described process is the trimen'c additionproduct obtainable from formaldehyde and acrylonitrile, i.e.hexahydro-1.3.5-triacrylyl s-triazine (see Ballauf and Wegler, Chem.Ber. 81 1948),

' ing and decorating of textile materials is variable. Thus,

it is of no importance whether the textile materials are pretreated withthe polyfunctional compounds, or whether these compounds are added tothe copolymer, or applied during the drying operation after printing ordecorating. Suitable thickeners for the purposes of pigment printing arethe known thickening agents such as gum tragacanth, alkali alginates,aqueous gasoline and aqueous oil emulsions. The formulation of theprinting paste is carried out, for instance, by intimately mixing theemulsions or solutions of the binder with the solutions of the thickenerand then stirring the pigment dyestuff into the resulting paste. Thepaste can be diluted with water.

Apart from the possibility of employing a great number of polymers asstarting materials the advantage of the process and printing paste ofthe invention resides in the simplicity and safety of its applicationsince volatile, inflammable solvents are avoided.

The main advantage of the novel printing paste, however, consists in theexcellent properties of the prints obtained which are distinctlysuperior to those obtained by the known printing processes, as regardsfastness to rubbing and washing. I

Instead of employing the printing paste and the printing process for theprinting of textile materials, it may also be applied for the printingand padding of paper. This possibility is of importance especially inthe production of Wall paper since wall paper which is fast to rubbingand washing is obtained.

The following examples shall serve to illustrate the invention withoutlimiting same; the parts given being Example 1 A mixture of:

(a) 70 parts of 1.1-dichloroethene and 30 parts of a-chloro butylacrylate are emulsified in 150 parts of the aqueous solution of 3 partsof the sodium salt of the sulfonic acids obtained by sulfochlorinationof long chain paralfins. The polymerization is activated by addition of05 part of the sodium salt of the sulfinic acids of long chain paraffinsand 2 parts of n/ 11-1 80 After polymerizing at 20 C. for 20 hours, alatex of a copolymer content of 39.5 percent is obtained in a yield of100 percent.

(b) The adjustment of the printing paste is carried out by stirring 35parts of this latex into a mixture of parts of alginate thickener(25:1000) and 12 parts of turpentine, which has previously been mixedwith the acid dimethylamine salt of oleic acid as emulsifier. Into thispaste 15 parts of Helio Fast Blue BL paste percent) (SchultzFarbstofftabellen, vol. I, 7th edition, No. 1188) are introduced withstirring, and 15 parts of a percent weakly acetic acid aqueous solutionof hexamethylene diamine are added thereto (preferably an excessquantity of 10 percent calculated on the amount of the acetic acid isused). The mixture is then adjusted with water to 100 parts.

The prints obtained on cotton fabrics with this printing paste show,after condensing at 140l45 C., excellent fastness to rubbing and washingand a soft feel.

Example 2 (a) A mixture of parts of butadiene, parts of methylmethacrylate and 30 parts of or-ethyl acrolein are emulsified in 150parts of an aqueous solution of 3 parts of the sodium salt of sulfonicacids obtained by sulfochlorination of long chain parafiins. Thepolymerization is activated by addition of 0.5 part of the sodium saltof the sulfinic acids of long chain parafiins and 2 parts of n/1H SOAfter polymerizing at 18 C. for 24 hours a latex of a polymer content of37.5% is obtained.

(b) The adjustment of the printing paste is carried out by adding 35parts of this latex to a mixture of 35' parts of turpentine and 2 partsof benzyl-o-hydroxy-diphenyl-polyglycol-ether with intimate mixing. Intothis paste 20 parts of Naphthol AS/ITR (Schultz Farbstolftabellen, vol.I, 7th edition, No. (paste 20 percent) are introduced with stirring. 10parts of the hexamethylene diamine solution described in Example 1 arethen added.

(c) Instead of the above cross-linking agents 15 parts of a 10 percentaqueous solution of the acetate of a basic polyurea prepared from 0.2mol of diethylene triamine, 0.8 mol of 'yxy-diamino dipropylmethylamine,1.0 mol of hexane diisoeyanate,

may be employed. Since thickening is already brought about by thisproduct to a certain degree, 30 parts only of turpentine have still tobe added.

The prints obtained with this priniting paste are steamed; they areexcellently fast to washing and rubbing.

Example 3 A copolymer emulsion is prepared from 20 parts ofacrylonitrile, parts of 1.1-dichloroethene and 20 parts of acrylic acidmonobutylamide as described in Example 1. The latex (40 percent)obtained is used for preparing a printing paste according to Example 1.Instead of the acetic acid hexamethylene diamine solution indicated inExample 1 one of the following components are added:

(a) 15 parts of formaldehyde (30 percent), or

(b) 1.5 parts of hexahydro-1.3.S-triacrylyl-s-triazine (the trimericaddition product obtained from formaldehyde and acrylonitrile, seeBallauf and Wegler, Chem Ber. 81 (1948), page 527 et seq.), or

(c) 15 parts of the addition product of malonic acid and hexamethylenediisoeyanate (cf. French Patent 876,285), which liberates thediisocyanate on heating (at higher temperatures).

The prints prepared by means of the above cross-linking agents aredistinguished by good fastness properties.

Example 4 The mixture consisting of 25 parts of acrylonitrile, 35 partsof 1.1-dichloroethene, 30 parts of butyl acrylate and 5 parts ofmethacrylic acid is emulsified in 150 parts of an aqueous solution of 3parts of the sodium salt of the sulfonic acids of long chain parafiins.The polymerization process is activated by addition of 0.6 part of thesodium salt of the sulfinic acids of long chain paraflins and themixture is adjusted to a pH value below 5. After polymerizing at 20 C.for 20 hours, a copolymer emulsion of about 38.5 percent polymer contentis obtained which can be made into a paste by addition of concentratedammonia in known manner.

A printing paste is adjusted with the above emulsion according toExample lb; the cross-linking agent described in Example 1, i.e. theacetic acid hexamethylene diamine solution, however, is replaced by 1.5parts of hexahydro-l.3.S-triacrylyl-s-triazine (see Example 3b). Theprints obtained with this printing paste are distinguished by theirbrightness of shades and a soft feel. They are especially fast towashing and solvents such as tetrachloro ethene, dichloro ethylene andperchloro ethylene.

Example 5 A copolymer emulsion of 30 parts of butadiene, 50 parts ofmethyl methacrylate and 20 parts of a-cyano sorbinic-acid ethyl-ester isprepared by emulsifying the mixture of said reactants in a solution of 5parts of the sodium salt of dibutyl naphthalene sulfonic acid in partsof water with the addition of 0.4 part of sodium hydroxide, 0.5 part ofpotassium per. sulfate and 0.4 part of sodium hydrosulfite. Afterpolymerizing at 30 C. for 36 hours the monomers have completely reacted.A latex of a polymer content of 37.5 percent is obtained.

The formulation of a printing paste is carried out as described inExample 1]), however, 1.5 parts of hexahydro-l.3.S-triacrylyl-s-triazineare used as cross-linking agent instead of the hexamethylene diaminesolution. The prints obtained with this printing paste show on rayonstaple fabrics and cotton fabrics good fastness properties.

Example 6 A copolymer emulsion is prepared from 30 parts of butadiene,20 parts of styrene, 30 parts of butyl acrylate, 20 parts ofacrylonitrile and 3 parts of acrylamide as described in Example 1. Theemulsion (about 39 percent) obtained shows a rather high viscosity.

The formulation of a printing paste is carried out by adding to 40 partsof the above emulsion, 5 parts of a 20 percent aqueous solution ofbenzyl-p-hydroxy diphenyl polyglycol ether, 5 parts of methyl cellulose(70:1000), 15 parts of a 20 percent blue copper phthalocyanine dyestuffpaste, 1.5 parts of hexahydro-1.3.5- triacrylyl-s-triazine and 23.5parts of water. The prints obtained with this printing paste on cottonfabrics and rayon staple fabrics show good fastness properties afterfixing by steaming or condensing.

Example 7 The above mixture is slop-padded on rayon staple fabrics,cotton and other fabrics on a padding machine, dried in heatingapparatus at 110 C. in the usual manner and thereby fixed to the fibre.The dyeings thus obtained are distinguished by very good fastness torubbing and washing.

We claim:

1. An aqueous printing paste consisting essentially of an emulsion of awater-insoluble copolymer of at least one compound (a) corresponding tothe general formula wherein R stands for a radical selected from thegroup consisting of an aldehyde group, a carboxylic group and acarbonamide group with at least one free hydrogen atom, R stands for aradical selected from the group consisting of hydrogen, methyl andethyl, and R" for a radical selected from the group consisting ofhydrogen and methyl; and at least one compound (11) selected from thegroup consisting of an alkyl acrylate and an alkyl methacrylate, thealkyls having at least four carbon atoms, and butadiene; apolyfunctional compound selected from the group consisting of 1) anacetic acid salt of hexamethylene diamine, (2)hexahydro-1,3,5-triacrylyls-triazine, and (3) an addition product of anorganic diisocyanate, which product will liberate said organicdiisocyanate at temperatures up to 200 C.; a pigment; and a thickeningagent.

2. An aqueous printing paste as claimed in claim 1, wherein thecopolymer consists essentially of at least one compound (a)corresponding to the general formula wherein R stands for a radicalselected from the group consisting of an aldehyde group, a carboxylicgroup and a carbonamide group with at least one free hydrogen atom, Rstands for a radical selected from the group consisting of hydrogen,methyl and ethyl, and R for a radical selected from the group consistingof hydrogen and methyl, and at least one compound (b) selected from thegroup consisting of an alkyl acrylate and an alkyl methacrylate, thealkyl having at least four carbon atoms, and butadiene; and a compoundselected from the group consisting of styrene, acrylonitrile,1,1-dichloroethene and an alkyl rnethacrylate, the alkyl group of whichhas at most 3 carbon atoms.

3. A printing paste consisting essentially of (1) an emulsion of acopolymer of methylmethacrylate, a-ethyl acrolein and butadiene, (2) theacetic acid salt of hexamethylene diamine, (3) a pigment, (4) athickening agent, and (5) water.

4. A printing paste consisting essentially of (1) an emulsion of acopolymer of acrylic acid monobutyl amide,

6 acrylonitrile, and 1,1-dichloroethene, (2) the addition product ofmalonic acid and hexamethylene diisocyanate, (3) a pigment, (4) athickening agent, and (5) water.

5. A printing paste consisting essentially of (1) an emulsion of acopolymer of butyl acrylate, acrylonitrile, 1,1-dichloroethene andmethacrylic acid, (2) hexahydro- 1,3,S-triacrylyl-s-triazine, (3) apigment, (4) a thickening agent and (5) water.

6. A printing paste consisting essentially of (1) an emulsion of acopolymer of acrylarnide, acrylonitrile, butyl-acrylate, butadiene andstyrene, (2) hexahydro- 1,3,5-triacrylyl-s-triazine, (3) a pigment, (4)a thickening agent, and (5) water.

7. A process of decorating a textile which comprises applying to saidtextile a printing paste having the composition of claim 1, and thenheating said textile for a time and at a temperature sufiicient to curethe resin,

whereby the latter is fixed to the textile.

8. A process of decorating a textile Which comprises applying to saidtextile a printing paste having the composition of claim 2, and thenheating said textile for a time and at a temperature sufiicient to curethe resin, whereby the latter is fixed to the textile.

9. A process of decorating a textile which comprises applying to saidtextile a printing paste having the composition of claim 3, and thenheating said textile for a time and at a temperature sufiicient to curethe resin, whereby the latter is fixed to the textile.

10. A process of decorating a textile which comprises applying to saidtextile a printing paste having the composition of claim 4, and thenheating said textile for a time and at a temperature sufficient to curethe resin, whereby the latter is fixed to the textile.

11. A process of decorating a textile which comprises applying to saidtextile a printing paste having the composition of claim 5, and thenheating said textile for a time and at a temperature sufficient to curethe resin, whereby the latter is fixed to the textile.

12. A process of decorating a textile Which comprises applying to saidtextile a printing paste having the composition of claim 6, and thenheating said textile for a time and at a temperature sufficient to curethe resin, whereby the latter is fixed to the textile.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Gams et al.: British Plastics, February 1943, pages 508-520.

1. AN AQUEOUS PRINTING PASTE CONSISTING ESSENTIALLY OF AN EMULSION OF AWATER-INSOLUBLE COPOLYMER OF AT LEAST ONE COMPOUND (A) CORRESPONDING TOTHE GENERAL FORMULA